Production of spirohydrocarbons



Patented Aug. 7, 1951 UNITED STATES PATENT OFFICE PRODUCTION OF SPIROI-IYDROCARBON S Louis Schmerling, Riverside, I11., assignor to UniversaiOil Products Company, Chicago, 111., a corporation of Delaware NoDrawing. Application July 25, 1947,

Serial No. 763,734

7 Claims. (Cl. 260-666) where R, R, R" and R are selected from the groupconsisting of hydrogen and alkyl radicals, X represents a halogen and nis an integer from 1 to 5 inclusive and the unsatisfied valences of thegroup are combined with a member of the group consisting of hydrogen andan alkyl radical.

Another specific embodiment of this invention relates to a process forproducing a spirohydrocarbon which comprises condensing an alpha,omega-dihaloalkane and a cycloalkadiene.

Yet another embodiment of this invention relates to a process forproducing a spirohydrocarbon which comprises reacting an alpha,ome-ga-dihaloalkane and an addition compound of a cycloalkadiene and analkali metal.

A further embodiment of this invention relates to a process forproducing a spirohydrocarbon which comprises reacting an alpha,omega-dihalo- -dia1ky1a1kane and a sodium addition compound of acycloalkadiene to form a diolefinic spirohydrocarbon having twoquaternary carbon atoms and hydrogenating said diolefinicspirohydrocarbon to form a saturated spirohydrocarbon having twoquaternary carbon atoms.

A still further embodiment of this invention relates to a process forproducing a spirohydrocarbon which comprises reacting 1,5-dibromo-3,3-dimethylpentane and disodium cyclopentadiene to form5,5-(33-dimethylpentamethylene) 1,3-cyclopentadiene.

This invention relates to a process for preparing hydrocarbonscontaining conjugated double bonds and a spiro carbon atom. Suchhydrocarbons which are new compositions of matter 2 are formed by thereactions indicated in the following equations:

The dihaloalkane in the above equation is1,5-dibromo-3,3-dimethylpentane. Other suitable dihaloalkanes are thosehaving the structure represented by R R a arm where R, R, R" and R' areselected from the group consisting of hydrogen and alkyl radicals, n isan integer from 1 to 5 inclusive, and X is halogen. The preferredcompounds are those in which R, R, R" and R are hydrogen, i. e.compounds in which the halogen atoms are attached to primary carbonatoms. Foorer yields are obtained when either (or both) halogen atom isattached to a secondary carbon atom and still lower yields are obtainedwith compounds con taining halogen attached to a tertiary carbon atom.The preferred value of n is 2 or 3. The preferred halogen is chlorine orbromine. In dihaloallganes represented by the above formula, theunsatisfied valence bonds are combined with a member of the groupconsisting of hydrogen and an alkyl group. p

Dihaloalkanes preferred as starting materials in this process areindicated by the following formula:

in which each of R R R R", R and R represents a member of the groupconsisting of hydrogen and alkyl radicals, X represents a halogen, andthe characters m and n are selected from the members of the groupconsisting of 0, 1, 2, and 3. The halogens generally preferred arechlorine and bromine. The characters m and n are such that their sum hasa value of from 0 to 4 and preferably of 1 or 2. When m and n are zeroFormula 2 is of essentially the same form as Formula 1.

A preferred starting material for this process is thus an alpha,omega-dihaloalkane in which a halogen atom, preferably chlorine orbromine, is combined with each of the two end carbon atoms of an alkanechain containing four or five carbon atoms. Such dihaloalkanes include1,5- dibromo 3,3 dimethylpentane, 1,4 dibromobutane, and1,5-dichloropentane.

Dihaloalkanes containing a quaternary carbon atom such as1,5-dichloro-3,3-dimethylpentane and the corresponding dibromoalkane maybe formed by condensing a monoolefin and a dihaloalkane in which one ofthe halogen atoms is attached to a tertiary carbon atom, and the otheris attached to a primary carbon atom, said condensation being carriedout in the presence of a Friedel-Crafts catalyst at a temperature offrom about -40 to about 100 C.

Good yields of such dihaloalkanes are obtained by condensing amonoolefin such as ethylene with a dihaloalkane in which the halogensare combined with one tertiary and one non-tertiary carbon atom. Thusethylene will condense with isoprene dihydrochloride (more exactly knownas 1,3-dichloro-3-methylbutane) in the presence of aluminum chloride andother Friedel-Crafts catalysts to form 1,5-dichloro-3,3dimethylpentane.

Cyclopentadiene is a diolefin which has two hydrogen atoms that arereadily replaced by sodium or by another alkali metal to form a sodiumaddition product of said cyclic diolefin which may be reacted withdihaloalkanes of the type described above to form a spirohydrocarbon.Thus reaction of cyclopentadiene sodium with1,5-dibromo-3,3-dimethylpentane yields 5,5-(3,3-

The condensation of a cycloalkadiene with an alpha, omega-dihaloalkanehaving at least four carbon atoms per molecule may be accomplished inseveral ways. One method consists in adding the diene to a solution ofsodium alkoxide in an alcohol such as ethyl alcohol and then adding thedihaloalkane. The addition of the diene to.

the solution of sodium alkoxide is preferably carried out at about 20 to25 C; Reaction with 1 the dihalide may be carried out at temperatures ofabout l0 to +100 C., preferablyat about the reflux temperature of thereaction mixture.

Another procedure consists in adding the diene to a solution of sodiumin'liquid ammonia and 1 then adding the dihalide. The reactionmay beBoth 5 4 the process of this invention although the data are notintroduced with the intention of limiting unduly the broad scope of theinvention.

Example I The condensation of Cyclopentadiene and 1,5-dibromo-3,3-dimethylpentane was carried out as follows in a glassreactor of 500 cc. capacity. Sodium metal (5 g., 0.21 mole) wasdissolved in 67 cc. of absolute alcohol (redistilled from sodium). Theresulting solution was cooled to 2 C. and 7 g. (0.11 mole) ofcyclopentadiene was added. A brown precipitate separated,1,5-dibroIno-3,3-dimethylpentane (25 g., 0.10 mole) was added and thestirred mixture was heated to 60 C. A White salt precipitated. Thetemperature was maintained at 6070 C. for two hours, the product wasthen cooled, water was added and the product was steam distilled. Therewas obtained 9 cc. of

Cut 2 was analyzed. 88.83; H, 11.17. Found: C, 86.77; H, 10.86. Reactionof the material (a diene) with air is in-: dicated.

Cut 2 yielded a maleic anhydride adduct.

Example II Cyclopentadiene (18. g., 0.27 mole). was added to a solutionof 10 g. (0.42 mole) of sodium in g. of liquid ammonia in a glass-linedreactor equipped with a, motor-driven stirrer and surrounded by asuitable cooling bath. 1,5-dibromo- 3,3-dimethylpentane (52 g., 0.20mole) was then added dropwise with stirring during one-half hour. Theblue color of the solution disappeared after about two-thirds of thedibromide had been added. The solution was stirred for an additionalone-half hour, water was added, and the organic product was taken up inether, washed,

Cut 4 crystallized when cooled to -78 C. It

yielded a maleic anhydride adduct, M. P. The adduct was analyzed. Calcd.for 0161121103; C, 73.80; H. 7.75. Found: C, 74.31; H, 7.83.

The hydrocarbon formed by the condensation of1,5-dibrorno-3,3di1nethylpentane and cyclopentadicne had the correctboiling point and 1 composition for 5,5-(3,3-dimethylpentamethylene)-1,3-cyclopentadiene and also formed a maleic anhydride adduct havingthe proper carben and hydrogen content. This condensation product of analpha, omega-dihaloalkane and a cycloalkadiene is a member of a newclass of 1 hydrocarbons, namely, a conjugated diolefin containing aspiro carbon atom. Also the hydro- Calcd. for C12H18Z c,

genation of such a conjugated cyclodiolefln containing a spiro carbonatom yields a saturated spirohydrocarbon. Some of the saturatedspirohydrocarbons which may be formed by this 6 which comprises reactingan alpha, omega-d1- halo- -dimethylalkane and a sodium addition compoundof a cycloalkadiene containing a methylene group attached to two doublebonded process also contained two quaternary carbon 5 carbon atoms toform a diolefinic spirohydroatoms, that is, a quaternary carbon atom inaddicarbon having two quaternary carbon atoms and tion to the spirocarbon atom. hydrogenating said diolefinic spirohydrocarbon to form asaturated spirohydrocarbon having two Example HI quaternary carbonatoms.

Reaction products obtained in Examples I and 3. A process for producinga spirohydrocarbon II and consisting essentially of dimethylpentawhichcomprises reacting 1,5-dibromo-3,3-dlmethylenecyclopentadiene werecombined and methylpentane and disodium cyclopentadiene to the resulting10.6 cc. of liquid hydrocarbon was form 5,5-(3,3-dimethylpentamethy1ene)-1,3-cydissolved in 11 cc. of n-pentane and hydrogenated clopentadiene.at a temperature of from 50 to 75 C. in the 15 4. A process forproducing a spirohydrocarbon presence of a nickel-diatomaceous earthcatalyst. which comprises reacting 1,5-dibromo-3,3-di- The hydrogenationproduct was filtered to sepmethylpentane and disodium cyclopentadiene toarate the pentane solution from the catalyst. form5,5-(3,3-dimethylpentamethylene)-1,3-cy- The pentane solution was thendistilled and sepclopentadiene, and hydrogenating the latter arated intofractions with the following propercompound to form8,8-dimethylspiro[4.5l-deties: cane.

A Below 2. 0 Below 175 41 g. (Pentane) 1 Determined with thermometer inliquid in test tube. 2 Slightly unstable to nitrating mixture.

Analysis of cut 4, Calcd. for 0121-122: C, 86.65; 5 5. A process forproducing a spirohydrocarbon H, 13.35. Found: C, 86.79; H, 13.11. whichcomprises reacting 1,5-dibromo-3,3-di

Analysis of cut 3. Found: C, 85.51; H, 12.20. methylpentane and disodiumcyclopentadiene in Fraction 4 consisted essentially of 8,8-diliquidammonia to form 5,5-(3,3-dimethylpentamethylspiro[4.5l-decane which mayalso be remethylene)-1,3-cyclopentadiene, and hydrogenferred to as1,1tetramethylene-4,4-dimethylcyating the latter compound to form8,8-dimethylclohexane. spiro [4.5] -decane.

The cyclic diolefins preferred for use in this 6. A process forproducing a spirohydrocarbon process are those containing a methylenegroup which comprises reacting 1,5-dibromo-3,3di- (that is, -CH2)attached to two doubly bonded methylpentane and disodium cyclopentadienein carbon atoms of the diolefin. Such cyclic diole- 45 the presence ofan alcohol and a sodium alkoxide fins include, for example,cyclopentadiene, 1.4- at a temperature of from about 10 to aboutcyclohexadiene, and the like. The hydrogen 100 0., to form5,5-(3,3-dimethylpentamethylatoms in this particular kind of methylenegroup one) -1,3-cyclopentadiene and hydrogenating the are replaceable byan alkali metal such as sodium, latter compound in the presence of anickel catpotassium, etc., and an alkali metal substituted alyst to form8,8-dimethylspiro[4.5l-decane. cyclic diolefin is formed which is hereinreferred '7. 5,5-(3,3-dimethylpentamethylene) 1,3 cyto as an alkalimetal addition compound of a clopentadiene. cycloalkadiene. LOUISSCHMERLING.

I claim as my invention:

1. A process for producing a spirohydrocar- REFERENCES CITED bon whichcomprises condensing an alkali metal h cycloalkadlene containing amethylene group atigi z rferences are of record in t e tached to twodouble bonded carbon atoms and me 0 15 a dihaloalkane having thestructure represented UNITED STATES PATENTS by the formula: Number NameDate R R 2,407,214 Birch et al Sept. 10, 1946 .ox OTHER REFERENCESMarvel et al.: Jour. Am. Chem. Soc., vol. 63, where R, R, R and R' areselected from the 55 3 -2 (1941) group consisting of hydrogen and alkylradicals, Thiele! Berlchte. VOL 53-71 901)- X represents a halogen and nis an integer from Taylor 8t Jour- Chem 702 1 to 5 inclusive and theunsatisfied valences of (1941)- the group Alder et al.: Annalen, vol.524, 164-6 (1936). Levitz et al.: Jour. Org. Chem., vol. 8, 253-255o-(w-o (1943).

I Meyer: Synthese der Kohlenstofi-Verbendunare combined with a member ofthe group congen, Erste Teil, 1. Halfte, pub. by Julius Springer sistingof hydrogen and an alkyl radical. (1938) Vienna, page 379.

2. A process for producing a spirohydrocarbon 76

1. A PROCESS FOR PRODUCING A SPIROHYDROCARBON WHICH COMPRISES CONDENSINGAN ALKALI METAL CYCLOALKADIENE CONTAINING A METHYLENE GROUP ATTACHED TOTWO DOUBLE BONDED CARBON ATOMS AND A DIHALOALKANE HAVING THE STRUCTUREREPRESENTED BY THE FORMULA: